JP2012190952A - Sealant for optical semiconductor device, cured sealant for optical semiconductor device, and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealant for optical semiconductor device having excellent transparency and capable of increasing the brightness of light taken out from an optical semiconductor device.SOLUTION: The sealant for optical semiconductor device contains a first silicon resin having an aryl group and an alkenyl group (excepting a silicon resin having a hydrogen atom bonded to a silicon atom), a second silicon resin having an aryl group and a hydrogen atom bonded to a silicon atom, silicon oxide particles subjected to surface treatment by an organic silicon compound, and a catalyst for hydrosilylation reaction. The cured sealant for optical semiconductor device has a refraction index of 1.450-1.470.

Description

  The present invention uses an encapsulant for optical semiconductor devices used for encapsulating optical semiconductor elements in an optical semiconductor device, a cured product of the encapsulant for optical semiconductor devices, and the encapsulant for optical semiconductor devices. The present invention relates to an optical semiconductor device.

  An optical semiconductor device such as a light emitting diode (LED) device has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.

  When an optical semiconductor element (for example, an LED), which is a light emitting element used in an optical semiconductor device, is in direct contact with the atmosphere, the light emission characteristics of the optical semiconductor element rapidly deteriorate due to moisture in the atmosphere or floating dust. For this reason, the said optical semiconductor element is normally sealed with the sealing compound for optical semiconductor devices.

  Patent Document 1 listed below includes an epoxy resin, a specific epoxy-modified organopolysiloxane, a curing agent, and inorganic oxide particles having a volume average particle diameter of 1 to 100 nm as an encapsulant for optical semiconductor devices. An epoxy resin composition is disclosed. Here, silicon dioxide particles are mentioned as the inorganic oxide particles.

JP 2009-227849 A

  When a light emitting element is sealed with a conventional sealing agent for optical semiconductor devices as described in Patent Document 1, the brightness of light extracted from the obtained optical semiconductor device may be low.

  An object of the present invention is to provide an encapsulant for optical semiconductor devices that is excellent in transparency and can increase the brightness of light extracted from the optical semiconductor device, a cured product of the encapsulant for optical semiconductor devices, and the optical semiconductor. It is providing the optical semiconductor device using the sealing agent for apparatuses.

  According to a wide aspect of the present invention, a first silicone resin having an aryl group and an alkenyl group (excluding a silicone resin having a hydrogen atom bonded to a silicon atom), and a hydrogen atom bonded to an aryl group and a silicon atom And a silicon oxide particle surface-treated with an organosilicon compound and a hydrosilylation reaction catalyst, and the cured product has a refractive index of 1.450 to 1.470. An encapsulant for optical semiconductor devices is provided.

  In a specific aspect of the encapsulant for optical semiconductor devices according to the present invention, the first silicone resin is a first silicone resin represented by the following formula (1A) and having an aryl group and an alkenyl group (provided that The second silicone resin is represented by the following formula (51A) and has a hydrogen atom bonded to an aryl group and a silicon atom. It is a silicone resin.

  In the above formula (1A), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 represent at least one aryl group, at least one represents an alkenyl group, and R1 to R6 other than the aryl group and the alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. .

  In the above formula (51A), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, R51 to R56 each represent at least one aryl group, at least one represents a hydrogen atom bonded to a silicon atom, and R51 to R51 other than an aryl group and a hydrogen atom bonded to a silicon atom R56 represents a hydrocarbon group having 1 to 8 carbon atoms.

  In another specific aspect of the encapsulant for optical semiconductor devices according to the present invention, the content ratios of aryl groups obtained from the following formula (X) in the first silicone resin and the second silicone resin are 10 respectively. More than mol% and less than 30 mol%.

  Content ratio of aryl group (mol%) = (average number of aryl groups contained in one molecule of the first silicone resin or the second silicone resin × molecular weight of the aryl group / the first silicone resin or the above Number average molecular weight of second silicone resin) × 100 Formula (X)

  In another specific aspect of the encapsulant for optical semiconductor devices according to the present invention, the organosilicon compound includes an organosilicon compound having a dimethylsilyl group, an organosilicon compound having a trimethylsilyl group, and an organosilicon having a polydimethylsiloxane group. It is at least one selected from the group consisting of compounds.

  The hardened | cured material of the sealing agent for optical semiconductor devices which concerns on this invention is a hardened | cured material obtained by hardening the sealing agent for optical semiconductor devices comprised according to this invention, The refractive index of this hardened | cured material is 1. .450 to 1.470.

  An optical semiconductor device according to the present invention includes an optical semiconductor element and a cured product of an optical semiconductor device sealant provided so as to seal the optical semiconductor element. Hardened | cured material is formed by hardening the sealing compound for optical semiconductor devices comprised according to this invention.

  The encapsulant for optical semiconductor devices according to the present invention includes a first silicone resin having an aryl group and an alkenyl group (excluding a silicone resin having a hydrogen atom bonded to a silicon atom), an aryl group and a silicon atom. Since it contains a second silicone resin having bonded hydrogen atoms, silicon oxide particles surface-treated with an organosilicon compound, and a catalyst for hydrosilylation reaction, a curing in which an encapsulant for optical semiconductor devices is further cured Since the refractive index of the product is 1.450 to 1.470, the sealant is excellent in transparency, and obtained when the optical semiconductor element is sealed with the sealant for optical semiconductor devices according to the present invention. The brightness of light extracted from the obtained optical semiconductor device can be increased.

FIG. 1 is a front sectional view showing an optical semiconductor device according to an embodiment of the present invention.

  Details of the present invention will be described below.

  The encapsulant for optical semiconductor devices according to the present invention includes a first silicone resin, a second silicone resin, silicon oxide particles, and a hydrosilylation reaction catalyst.

  The first silicone resin (excluding a silicone resin having a hydrogen atom bonded to a silicon atom) has an aryl group and an alkenyl group. The second silicone resin has an aryl group and a hydrogen atom bonded to a silicon atom. The silicon oxide particles are surface-treated with an organosilicon compound.

  Moreover, the refractive index of the hardened | cured material after hardening of the sealing compound for optical semiconductor devices which concerns on this invention is 1.450-1.470. The “refractive index of the cured product” in the encapsulant for optical semiconductor devices according to the present invention is preferably a value in a cured product cured at 130 ° C. for 3 hours. This is because the sealant is generally cured at 80 to 170 ° C. for 0.5 to 12 hours. The “refractive index of the cured product” indicates a refractive index at a wavelength of 589 nm. The refractive index can be measured using a digital Abbe refractometer (manufactured by Elma) or the like.

  By adopting the above composition and setting the refractive index of the cured product to 1.450 to 1.470, the transparency of the encapsulant for optical semiconductor devices according to the present invention can be enhanced, and further according to the present invention. The brightness of light extracted from the optical semiconductor device using the encapsulant for optical semiconductor devices can be considerably increased.

  From the viewpoint of further increasing the brightness of light extracted from the optical semiconductor device, the first silicone resin is a first silicone resin represented by the formula (1A) and having an aryl group and an alkenyl group (provided that And the second silicone resin is represented by the formula (51A) and has an aryl group and a hydrogen atom bonded to a silicon atom. 2 is preferable. Furthermore, from the viewpoint of further increasing the brightness of light extracted from the optical semiconductor device, the content ratios of the aryl groups obtained from the following formula (X) in the first and second silicone resins are 10 mol% or more, It is preferable that it is less than 30 mol%.

  Content ratio of aryl group (mol%) = (average number of aryl groups contained in one molecule of the first silicone resin or the second silicone resin × molecular weight of the aryl group / the first silicone resin or the above Number average molecular weight of second silicone resin) × 100 Formula (X)

  That is, by using the specific first and second silicone resins represented by the formula (1A) or the formula (51A), the aryl group content is further 10 mol% or more and less than 30 mol%, respectively. By using the first and second silicone resins, the refractive index of the cured product of the sealant can be controlled to a more suitable range, and the brightness of the light extracted from the optical semiconductor device can be further increased.

  From the viewpoint of further increasing the brightness of the light extracted from the optical semiconductor device, the refractive index of the cured product is preferably 1.452 or more, and preferably 1.468 or less.

  By the way, the conventional sealant for optical semiconductor devices may crack in the sealant or peel off from the housing material or the like when used in a harsh environment that is repeatedly subjected to heating and cooling. There is.

  Moreover, in order to reflect the light which reached the back surface side of the light emitting element, an electrode plated with silver may be formed on the back surface of the light emitting element. When a crack occurs in the sealant or the sealant peels from the housing material, the silver-plated electrode is exposed to the atmosphere. In this case, the silver plating may be discolored by a corrosive gas such as hydrogen sulfide gas or sulfurous acid gas present in the atmosphere. When the color of the electrode changes, the reflectance decreases, which causes a problem that the brightness of the light emitted from the light emitting element decreases.

  For such a problem, from the viewpoint of suppressing a decrease in gas barrier properties of the sealant, the first silicone resin is represented by the formula (1A) and has a first aryl group and an alkenyl group. It is preferably a silicone resin (excluding a silicone resin having a hydrogen atom bonded to a silicon atom), and the second silicone resin is represented by the formula (51A) and bonded to an aryl group and a silicon atom. It is preferable that it is the 2nd silicone resin which has a hydrogen atom.

  Hereinafter, the detail of each component contained in the sealing compound for optical semiconductor devices which concerns on this invention is demonstrated.

(First silicone resin)
The first silicone resin (excluding the silicone resin having a hydrogen atom bonded to a silicon atom) contained in the encapsulant for optical semiconductor devices according to the present invention has an aryl group and an alkenyl group.

  The first silicone resin is a first silicone resin that does not have a hydrogen atom bonded to a silicon atom and has an aryl group and an alkenyl group. The first silicone resin is different from the second silicone resin because it does not have a hydrogen atom bonded to a silicon atom. Each of the aryl group and the alkenyl group is preferably directly bonded to the silicon atom. As said aryl group, an unsubstituted phenyl group and a substituted phenyl group are mentioned. The carbon atom in the carbon-carbon double bond of the alkenyl group may be bonded to the silicon atom, and the carbon atom different from the carbon atom in the carbon-carbon double bond of the alkenyl group is in the silicon atom. It may be bonded. As for the 1st silicone resin, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further increasing the brightness of light extracted from the optical semiconductor device and obtaining a sealing agent that is further excellent in gas barrier properties, the first silicone resin is represented by the following formula (1A). The silicone resin is preferably used. However, a silicone resin other than the first silicone resin represented by the following formula (1A) may be used as the first silicone resin.

In the above formula (1A), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 represent at least one aryl group, at least one represents an alkenyl group, and R1 to R6 other than the aryl group and the alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. . In the above formula (1A), the structural unit represented by (R4R5SiO _2/2 ) and the structural unit represented by (R6SiO _3/2 ) may each have an alkoxy group, and have a hydroxy group. You may have.

  The above formula (1A) represents an average composition formula. The hydrocarbon group in the above formula (1A) may be linear or branched. R1 to R6 in the above formula (1A) may be the same or different.

In the above formula (1A), the oxygen atom part in the structural unit represented by (R4R5SiO _2/2 ) and the oxygen atom part in the structural unit represented by (R6SiO _3/2 ) each form a siloxane bond. An oxygen atom part, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.

  In general, in each structural unit of the above formula (1A), the content of alkoxy groups is small, and the content of hydroxy groups is also small. In general, when an organosilicon compound such as an alkoxysilane compound is hydrolyzed and polycondensed in order to obtain a first silicone resin, most of the alkoxy groups and hydroxy groups are converted into partial skeletons of siloxane bonds. Because. That is, most of oxygen atoms of the alkoxy group and oxygen atoms of the hydroxy group are converted into oxygen atoms forming a siloxane bond. When each structural unit of the above formula (1A) has an alkoxy group or a hydroxy group, it indicates that a slight amount of unreacted alkoxy group or hydroxy group that has not been converted into a partial skeleton of a siloxane bond remains. The same applies to the case where each structural unit of formula (51A) described later has an alkoxy group or a hydroxy group.

  In the above formula (1A), examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. From the viewpoint of further improving gas barrier properties, the alkenyl group in the first silicone resin and the alkenyl group in the above formula (1A) are preferably vinyl groups or allyl groups, and more preferably vinyl groups.

  It does not specifically limit as a C1-C8 hydrocarbon group in the said Formula (1A), For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, Examples thereof include n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group and cyclohexyl group.

  It is preferable that the content ratio of the aryl group calculated | required from the following formula (X1) in the said 1st silicone resin is 10 mol% or more and less than 30 mol%. When the content ratio of the aryl group is 10 mol% or more and less than 30 mol%, the refractive index of the cured product can be controlled to a more suitable range, and the brightness of light extracted from the optical semiconductor device can be further increased. Can do. From the viewpoint of further increasing the brightness of light extracted from the optical semiconductor device, the content ratio of the aryl group is more preferably 15 mol% or more, more preferably 29 mol% or less, and further preferably 25 mol% or less. .

  Content ratio of aryl group (mol%) = (average number of aryl groups contained in one molecule of the first silicone resin whose average composition formula is represented by formula (1A) × molecular weight of aryl group / average composition formula Number average molecular weight of first silicone resin represented by formula (1A)) × 100 Formula (X1)

In the first silicone resin represented by the above formula (1A), the structural unit represented by (R4R5SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) is represented by the following formula (1-2). That is, a structure in which one of oxygen atoms bonded to a silicon atom in a bifunctional structural unit constitutes a hydroxy group or an alkoxy group may be included.

(R4R5SiXO _1/2 ) (Formula (1-2))

The structural unit represented by (R4R5SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-b), and is further represented by the following formula (1-2b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R4 and R5 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R4R5SiO _2/2 ). Specifically, when the alkoxy group is converted into a partial skeleton of a siloxane bond, the structural unit represented by (R4R5SiO _2/2 ) is a broken line of the structural unit represented by the following formula (1-b) The part enclosed by is shown. When an unreacted alkoxy group remains, or when the alkoxy group is converted to a hydroxy group, the structural unit represented by (R4R5SiO _2/2 ) having the remaining alkoxy group or hydroxy group has the following formula: The part enclosed with the broken line of the structural unit represented by (1-2-b) is shown. In the structural unit represented by the following formula (1-b), the oxygen atom in the Si—O—Si bond forms a siloxane bond with the adjacent silicon atom, and the adjacent structural unit and oxygen atom Sharing. Accordingly, one oxygen atom in the Si—O—Si bond is defined as “O _1/2 ”.

  In the above formulas (1-2) and (1-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R4 and R5 in the above formulas (1-b), (1-2) and (1-2b) are the same groups as R4 and R5 in the above formula (1A).

In the first silicone resin represented by the above formula (1A), the structural unit represented by (R6SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following formula (1-3) or (1 -4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a bond to a silicon atom in a trifunctional structural unit One of the oxygen atoms may include a structure constituting a hydroxy group or an alkoxy group.

(R6SiX ₂ O _1/2 ) Formula (1-3)
(R6SiXO _2/2 ) Formula (1-4)

The structural unit represented by (R6SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-c), and further includes the following formula (1-3-c) or (1 The part enclosed with the broken line of the structural unit represented by -4-c) may be included. That is, a structural unit having a group represented by R6 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R6SiO _3/2 ).

  In the above formulas (1-3), (1-3-c), (1-4) and (1-4-c), X represents OH or OR, and OR represents a linear or branched group. An alkoxy group having 1 to 4 carbon atoms is represented. R6 in the above formulas (1-c), (1-3), (1-3-c), (1-4) and (1-4-c) is the same as R6 in the above formula (1A). It is the basis of.

  The above formulas (1-b) and (1-c), formulas (1-2) to (1-4), and formulas (1-2b), (1-3-c) and (1-4- In c), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, and an isobutoxy group. , Sec-butoxy group and t-butoxy group.

In the above formula (1A), the lower limit of a / (a + b + c) is 0, and the upper limit is 0.50. When a / (a + b + c) satisfies the above upper limit, the heat resistance of the sealant can be further increased, and peeling of the sealant can be further suppressed. In said formula (1A), the preferable upper limit of a / (a + b + c) is 0.45, and a more preferable upper limit is 0.40. When a is 0 and a / (a + b + c) is 0, there is no structural unit (R1R2R3SiO _1/2 ) in the above formula (1A).

  In the above formula (1A), the lower limit of b / (a + b + c) is 0.40, and the upper limit is 1.0. When b / (a + b + c) satisfies the above lower limit, the cured product of the sealant does not become too hard, and cracks are hardly generated in the sealant. In said formula (1A), the minimum with preferable b / (a + b + c) is 0.50.

In the above formula (1A), the lower limit of c / (a + b + c) is 0, and the upper limit is 0.50. When c / (a + b + c) satisfies the above upper limit, it is easy to maintain an appropriate viscosity as a sealant, and adhesion can be further enhanced. In the above formula (1A), the preferable upper limit of c / (a + b + c) is 0.45, the more preferable upper limit is 0.40, and the still more preferable upper limit is 0.35. In addition, when c is 0 and c / (a + b + c) is 0, the structural unit of (R6SiO _3/2 ) does not exist in the above formula (1A).

  C / (a + b + c) in the above formula (1A) is preferably 0. That is, the first silicone resin represented by the above formula (1A) is preferably the first silicone resin represented by the following formula (1Aa). As a result, cracks are less likely to occur in the sealant, and the sealant is more difficult to peel from the housing material or the like.

  In the above formula (1Aa), a and b satisfy a / (a + b) = 0 to 0.50 and b / (a + b) = 0.50 to 1.0, and at least one of R1 to R5 is aryl. R4 to R5 each represents an alkenyl group, and R1 to R5 other than the aryl group and the alkenyl group each represent a hydrocarbon group having 1 to 8 carbon atoms.

  In said formula (1Aa), the preferable upper limit of a / (a + b) is 0.45, and a more preferable upper limit is 0.40. In said formula (1Aa), the preferable minimum of b / (a + b) is 0.55, and a more preferable minimum is 0.60.

When the first silicone resin is subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although the above formula shows a slight variation depending on the type of substituent. The peak corresponding to the structural unit represented by (R1R2R3SiO _1/2 ) _a in (1A) appears in the vicinity of +10 to −5 ppm, and (R4R5SiO _2/2 ) _b and (1-2) in the above formula (1A) ) Appearing in the vicinity of −10 to −50 ppm, (R6SiO _3/2 ) _c in the above formula (1A), and (1-3) and (1-4) Each peak corresponding to the functional structural unit appears in the vicinity of −50 to −80 ppm.

Therefore, the ratio of each structural unit in the above formula (1A) can be measured by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.

However, in the case where the structural unit in the formula (1A) cannot be distinguished by the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also the ¹ H-NMR measurement result. Can be used to distinguish the proportion of each structural unit in the above formula (1A).

(Second silicone resin)
The second silicone resin contained in the encapsulant for optical semiconductor devices according to the present invention has an aryl group and a hydrogen atom bonded to a silicon atom. The aryl group is preferably directly bonded to the silicon atom. Hydrogen atoms are directly bonded to silicon atoms. As for the 2nd silicone resin, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further increasing the brightness of light extracted from the optical semiconductor device and obtaining a sealant that is further excellent in gas barrier properties, the second silicone resin is a second resin represented by the following formula (51A). The silicone resin is preferably used. However, a silicone resin other than the second silicone resin represented by the following formula (51A) may be used as the second silicone resin.

In the above formula (51A), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, R51 to R56 each represent at least one aryl group, at least one represents a hydrogen atom bonded to a silicon atom, and R51 to R51 other than an aryl group and a hydrogen atom bonded to a silicon atom R56 represents a hydrocarbon group having 1 to 8 carbon atoms. In the formula (51A), the structural unit represented by (R54R55SiO _2/2 ) and the structural unit represented by (R56SiO _3/2 ) may each have an alkoxy group, You may have.

  The above formula (51A) represents an average composition formula. The hydrocarbon group in the above formula (51A) may be linear or branched. R51 to R56 in the above formula (51A) may be the same or different.

In the formula (51A), the oxygen atom part in the structural unit represented by (R54R55SiO _2/2 ) and the oxygen atom part in the structural unit represented by (R56SiO _3/2 ) each form a siloxane bond. An oxygen atom part, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.

  It does not specifically limit as a C1-C8 hydrocarbon group in the said Formula (51A), For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, vinyl group and allyl group Is mentioned.

From the viewpoint of enhancing the curability of the sealant and further suppressing cracking and peeling in the thermal cycle, the structural unit represented by (R51R52R53SiO _1/2 ) in the above formula (51A) is such that R51 is a silicon atom. It is preferable that the hydrogen atom couple | bonded with and R52 and R53 contain the structural unit which represents a hydrogen atom, an aryl group, or a C1-C8 hydrocarbon group. The structural unit represented by (R51R52R53SiO _1/2 ) in the above formula (51A) represents a hydrogen atom in which R51 is bonded to a silicon atom, and R52 and R53 represent an aryl group or a hydrocarbon group having 1 to 8 carbon atoms. It is more preferable that the structural unit to represent is included.

That is, in the above formula (51A), the structural unit represented by (R51R52R53SiO _1/2 ) preferably includes a structural unit represented by the following formula (51-a). The structural unit represented by (R51R52R53SiO _1/2 ) may include only the structural unit represented by the following formula (51-a), and the structural unit represented by the following formula (51-a) and the following And a structural unit other than the structural unit represented by Formula (51-a).

  In said formula (51-a), R52 and R53 represent a hydrogen atom, an aryl group, or a C1-C8 hydrocarbon group, respectively. R52 and R53 each preferably represent an aryl group or a hydrocarbon group having 1 to 8 carbon atoms.

From the viewpoint of enhancing the curability of the sealant and further suppressing cracking and peeling in the thermal cycle, it is represented by (R51R52R53SiO _1/2 ) in 100 mol% of all structural units in the above formula (51A). A structural unit in which R51 represents a hydrogen atom bonded to a silicon atom, and R52 and R53 represent a hydrogen atom, an aryl group, or a hydrocarbon group having 1 to 8 carbon atoms (in the above formula (51-a)). The proportion of the structural unit represented is preferably 5 mol% or more, more preferably 10 mol% or more, preferably 50 mol% or less, more preferably 45 mol% or less.

  It is preferable that the content ratio of the aryl group calculated | required from the following formula (X51) in the said 2nd silicone resin is 10 mol% or more and less than 30 mol%. When the content ratio of the aryl group is 10 mol% or more and less than 30 mol%, the refractive index of the cured product can be controlled to a more suitable range, and the brightness of light extracted from the optical semiconductor device can be further increased. Can do. From the viewpoint of further increasing the brightness of light extracted from the optical semiconductor device, the content ratio of the aryl group is more preferably 15 mol% or more, more preferably 29 mol% or less, and further preferably 25 mol% or less. .

  Content ratio of aryl group (mol%) = (average number of aryl groups contained in one molecule of the second silicone resin whose average composition formula is represented by the above formula (51A) × molecular weight of aryl group / average composition formula Is the number average molecular weight of the second silicone resin represented by the above formula (51A)) × 100 Formula (X51)

In the second silicone resin represented by the above formula (51A), the structural unit represented by (R54R55SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) is represented by the following formula (51-2). That is, a structure in which one of oxygen atoms bonded to a silicon atom in a bifunctional structural unit constitutes a hydroxy group or an alkoxy group may be included.

(R54R55SiXO _1/2 ) Formula (51-2)

The structural unit represented by (R54R55SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-b), and is further represented by the following formula (51-2-b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R54 and R55 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R54R55SiO _2/2 ).

  In the above formulas (51-2) and (51-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R54 and R55 in the above formulas (51-b), (51-2) and (51-2-b) are the same groups as R54 and R55 in the above formula (51A).

In the second silicone resin represented by the above formula (51A), the structural unit represented by (R56SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following formula (51-3) or (51 -4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a bond to a silicon atom in a trifunctional structural unit One of the oxygen atoms may include a structure constituting a hydroxy group or an alkoxy group.

(R56SiX ₂ O _1/2 ) (Formula (51-3)
(R56SiXO _2/2 ) Formula (51-4)

The structural unit represented by (R56SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-c), and further includes the following formula (51-3-c) or (51 The part enclosed with the broken line of the structural unit represented by -4-c) may be included. That is, a structural unit having a group represented by R56 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R56SiO _3/2 ).

  In the above formulas (51-3), (51-3-c), (51-4) and (51-4-c), X represents OH or OR, and OR represents a linear or branched group. An alkoxy group having 1 to 4 carbon atoms is represented. R56 in the above formulas (51-c), (51-3), (51-3-c), (51-4) and (51-4-c) is the same as R56 in the above formula (51A). It is the basis of.

  The above formulas (51-b) and (51-c), formulas (51-2) to (51-4), and formulas (51-2-b), (51-3-c), (51-4-) In c) and (51-5-d), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, and n-butoxy. Group, isopropoxy group, isobutoxy group, sec-butoxy group and t-butoxy group.

  In the above formula (51A), the lower limit of p / (p + q + r) is 0.05, and the upper limit is 0.50. When p / (p + q + r) satisfies the above upper limit, the heat resistance of the sealant can be further increased, and peeling of the sealant can be further suppressed. In said formula (51A), the preferable minimum of p / (p + q + r) is 0.10, and a more preferable upper limit is 0.45.

  In the above formula (51A), the lower limit of q / (p + q + r) is 0.05, and the upper limit is 0.50. When q / (p + q + r) satisfies the above lower limit, the cured product of the sealant does not become too hard, and cracks are hardly generated in the sealant. When q / (p + q + r) satisfies the above upper limit, the gas barrier property of the sealant is further enhanced. In said formula (51A), the preferable minimum of q / (p + q + r) is 0.10, and a more preferable upper limit is 0.45.

  In the above formula (51A), the lower limit of r / (p + q + r) is 0.20, and the upper limit is 0.80. When r / (p + q + r) satisfies the above lower limit, the hardness of the encapsulant is increased, the adhesion of scratches and dust can be prevented, the heat resistance of the encapsulant is increased, and the cured product of the encapsulant in a high temperature environment It becomes difficult to reduce the thickness. When r / (p + q + r) satisfies the above upper limit, it is easy to maintain an appropriate viscosity as a sealant, and adhesion can be further enhanced.

For the second silicone resin, when ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) is performed with reference to tetramethylsilane (hereinafter referred to as TMS), although some variation is observed depending on the type of substituent, the above formula The peak corresponding to the structural unit represented by (R51R52R53SiO _1/2 ) _p in (51A) appears in the vicinity of +10 to −5 ppm, and (R54R55SiO _2/2 ) _q and (51-2) in the above formula (51A). ) Appearing in the vicinity of −10 to −50 ppm, and (R56SiO _3/2 ) _r in the above formula (51A) and three of (51-3) and (51-4) Each peak corresponding to the functional structural unit appears in the vicinity of −50 to −80 ppm.

Therefore, the ratio of each structural unit in the above formula (51A) can be measured by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.

However, in the case where the structural unit in the formula (51A) cannot be identified by the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also the ¹ H-NMR measurement result. Can be used to distinguish the proportion of each structural unit in the above formula (51A).

  The content of the second silicone resin is preferably 10 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the first silicone resin. When the content of the first and second silicone resins is within this range, a sealant that is more excellent in gas barrier properties can be obtained. From the viewpoint of obtaining a sealant that is further excellent in gas barrier properties, the more preferable lower limit of the content of the second silicone resin is 30 parts by weight, and still more preferable lower limit with respect to 100 parts by weight of the first silicone resin. Is 50 parts by weight, a more preferred upper limit is 300 parts by weight, and a still more preferred upper limit is 200 parts by weight.

(Other properties of the first and second silicone resins and their synthesis methods)
The content of alkoxy groups in the first and second silicone resins is preferably 0.5 mol% or more, more preferably 1 mol% or more, preferably 10 mol% or less, more preferably 5 mol% or less. . When the content of the alkoxy group is not less than the above lower limit, the adhesion of the sealant is increased. When the content of the alkoxy group is not more than the above upper limit, the storage stability of the first and second silicone resins and the sealant is increased, and the heat resistance of the sealant is further increased.

  The content of the alkoxy group means the amount of the alkoxy group contained in the average composition formula of the first and second silicone resins.

  The first and second silicone resins preferably do not contain silanol groups. When the first and second silicone resins do not contain a silanol group, the storage stability of the first and second silicone resins and the sealant is increased. The silanol group can be reduced by heating under vacuum. The content of silanol groups can be measured using infrared spectroscopy.

  The preferable lower limit of the number average molecular weight (Mn) of the first and second silicone resins is 500, the more preferable lower limit is 800, the still more preferable lower limit is 1000, the preferable upper limit is 50000, and the more preferable upper limit is 15000. When the number average molecular weight satisfies the above preferable lower limit, the volatile components are reduced at the time of thermosetting, and the thickness of the cured product of the sealant is hardly reduced under a high temperature environment. When the number average molecular weight satisfies the above preferable upper limit, viscosity adjustment is easy.

  The number average molecular weight (Mn) is a value obtained by using polystyrene as a standard substance using gel permeation chromatography (GPC). The number average molecular weight (Mn) was measured using two measuring devices manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: Tetrahydrofuran, standard substance: polystyrene) means a value measured.

  The method for synthesizing the first and second silicone resins is not particularly limited, and examples thereof include a method in which an alkoxysilane compound is hydrolyzed and subjected to a condensation reaction, and a method in which a chlorosilane compound is hydrolyzed and condensed. Especially, the method of hydrolyzing an alkoxysilane compound from a viewpoint of control of reaction is preferable.

  Examples of the method for hydrolyzing and polycondensing the alkoxysilane compound include a method of reacting in the presence of an alkoxysilane compound, water and an acidic catalyst or a basic catalyst. Further, the disiloxane compound may be hydrolyzed and used.

  Examples of the organosilicon compound for introducing an aryl group into the first and second silicone resins include triphenylmethoxysilane, triphenylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyl (phenyl) dimethoxysilane, and Examples thereof include phenyltrimethoxysilane.

  Examples of the organosilicon compound for introducing an alkenyl group into the first silicone resin include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, methoxydimethylvinylsilane, vinyldimethylethoxysilane, and 1,3-divinyl- Examples include 1,1,3,3-tetramethyldisiloxane.

  Examples of organosilicon compounds for introducing hydrogen atoms bonded to silicon atoms into the second silicone resin include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and 1,1,3,3. -Tetramethyldisiloxane and the like.

  Examples of other organosilicon compounds that can be used to obtain the first and second silicone resins include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and isopropyl (methyl) dimethoxysilane. Cyclohexyl (methyl) dimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane.

  Examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides of inorganic acids and derivatives thereof, and acid anhydrides of organic acids and derivatives thereof.

  Examples of the inorganic acid include hydrochloric acid, phosphoric acid, boric acid, and carbonic acid. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid and oleic acid. Is mentioned.

  Examples of the basic catalyst include alkali metal hydroxides, alkali metal alkoxides, and alkali metal silanol compounds.

  Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and cesium hydroxide. Examples of the alkali metal alkoxide include sodium-t-butoxide, potassium-t-butoxide, and cesium-t-butoxide.

  Examples of the alkali metal silanol compound include a sodium silanolate compound, a potassium silanolate compound, and a cesium silanolate compound. Of these, a potassium-based catalyst or a cesium-based catalyst is preferable.

(Catalyst for hydrosilylation reaction)
The hydrosilylation reaction catalyst contained in the encapsulant for optical semiconductor devices according to the present invention includes an alkenyl group in the first silicone resin and a hydrogen atom bonded to a silicon atom in the second silicone resin. Is a catalyst for hydrosilylation reaction.

  As the hydrosilylation reaction catalyst, various catalysts that cause the hydrosilylation reaction to proceed can be used. As for the said catalyst for hydrosilylation reaction, only 1 type may be used and 2 or more types may be used together.

  Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Since the transparency of the sealant can be increased, a platinum-based catalyst is preferable.

  Examples of the platinum-based catalyst include platinum powder, chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex or a platinum-olefin complex is preferable.

  Examples of the alkenylsiloxane in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethyl-1,3,5. , 7-tetravinylcyclotetrasiloxane and the like. Examples of the olefin in the platinum-olefin complex include allyl ether and 1,6-heptadiene.

  Since the stability of the platinum-alkenylsiloxane complex and platinum-olefin complex can be improved, alkenylsiloxane, organosiloxane oligomer, allyl ether or olefin is added to the platinum-alkenylsiloxane complex or platinum-olefin complex. Is preferred. The alkenylsiloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. The organosiloxane oligomer is preferably a dimethylsiloxane oligomer. The olefin is preferably 1,6-heptadiene.

  From the viewpoint of further suppressing the decrease in luminous intensity when used in a harsh environment under high temperature and high humidity, and further suppressing discoloration of the sealant, the hydrosilylation reaction catalyst is An alkenyl complex of platinum is preferable. From the viewpoint of further suppressing the decrease in luminous intensity when used in a state of being energized in a severe environment under high temperature and high humidity, and further suppressing discoloration of the sealant, the platinum alkenyl complex is: It is preferably a platinum alkenyl complex obtained by reacting chloroplatinic acid hexahydrate with 6 equivalents or more of a bifunctional or higher alkenyl compound. In this case, the platinum alkenyl complex is a reaction product of chloroplatinic acid hexahydrate and 6 equivalents or more of a bifunctional or higher alkenyl compound. Moreover, the transparency of the sealant can be increased by using the platinum alkenyl complex. As for the said platinum alkenyl complex, only 1 type may be used and 2 or more types may be used together.

It is preferable to use the chloroplatinic acid hexahydrate (H ₂ PtCl ₆ .6H ₂ O) as a platinum raw material for obtaining the platinum alkenyl complex.

  Examples of the bifunctional or higher alkenyl compound of 6 equivalents or more for obtaining the platinum alkenyl include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-dimethyl- Examples include 1,3-diphenyl-1,3-divinyldisiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

  Regarding the “equivalent” in the bifunctional or higher alkenyl compound of 6 equivalents or more, the equivalent weight of 1 mol of the bifunctional or higher alkenyl compound is 1 equivalent to 1 mol of the chloroplatinic acid hexahydrate. . It is preferable that the bifunctional or higher alkenyl compound having 6 equivalents or more is 50 equivalents or less.

  Examples of the solvent used to obtain the platinum alkenyl complex include alcohol solvents such as methanol, ethanol, 2-propanol, and 1-butanol. Aromatic solvents such as toluene and xylene may be used. As for the said solvent, only 1 type may be used and 2 or more types may be used together.

  In order to obtain the platinum alkenyl complex, a monofunctional vinyl compound may be used in addition to the above components. Examples of the monofunctional vinyl compound include trimethoxyvinylsilane, triethoxyvinylsilane, and vinylmethyldimethoxysilane.

  Regarding the reaction product of chloroplatinic acid hexahydrate and 6 equivalents or more of bifunctional or higher alkenyl compound, platinum element and 6 equivalents or more of bifunctional or higher alkenyl compound are covalently bonded or distributed. Or are covalently bonded and coordinated.

  In the sealant, the content of the catalyst for hydrosilylation reaction is preferably 0.01 ppm or more and 1000 ppm or less in terms of weight units of metal atoms (in the case of platinum alkenyl complexes, platinum atoms). When the content of the hydrosilylation reaction catalyst is 0.01 ppm or more, it is easy to sufficiently cure the sealant. When the content of the catalyst for hydrosilylation reaction is 1000 ppm or less, the problem of coloring the cured product hardly occurs. The content of the hydrosilylation catalyst is more preferably 1 ppm or more, and more preferably 500 ppm or less.

(Silicon oxide particles)
The encapsulant for optical semiconductor devices according to the present invention further contains silicon oxide particles. By using the silicon oxide particles, the viscosity of the sealant before curing can be adjusted to an appropriate range without impairing the heat resistance and light resistance of the cured product of the sealant. Therefore, the handleability of the sealing agent can be improved. The silicon oxide particles are surface-treated with an organosilicon compound. By this surface treatment, the dispersibility of the silicon oxide particles becomes very high, and the decrease in the viscosity due to the increase in the temperature of the sealant before curing can be further suppressed.

  The primary particle diameter of the silicon oxide particles is preferably 5 nm or more, more preferably 8 nm or more, preferably 200 nm or less, more preferably 150 nm or less. When the primary particle diameter of the silicon oxide particles is not less than the above lower limit, the dispersibility of the silicon oxide particles is further increased, and the transparency of the cured product of the sealant is further increased. When the primary particle diameter of the silicon oxide particles is not more than the above upper limit, it is possible to sufficiently obtain the effect of increasing the viscosity at 25 ° C. and to suppress the decrease in the viscosity due to the temperature increase.

  The primary particle diameter of the silicon oxide particles is measured as follows. The cured product of the encapsulant for optical semiconductor devices is observed using a transmission electron microscope (trade name “JEM-2100”, manufactured by JEOL Ltd.). The size of the primary particles of 100 silicon oxide particles in the visual field is measured, and the average value of the measured values is defined as the primary particle diameter. The primary particle diameter means an average value of the diameters of the silicon oxide particles when the silicon oxide particles are spherical, and an average value of the major diameters of the silicon oxide particles when the silicon oxide particles are non-spherical.

The BET specific surface area of the silicon oxide particles is preferably 30 m ² / g or more, and preferably 400 m ² / g or less. When the BET specific surface area of the silicon oxide particles is 30 m ² / g or more, the viscosity of the sealant at 25 ° C. can be controlled within a suitable range, and a decrease in viscosity due to a temperature rise can be suppressed. When the BET specific surface area of the silicon oxide particles is 400 m ² / g or less, the aggregation of the silicon oxide particles hardly occurs, the dispersibility can be increased, and the transparency of the cured product of the sealant is further increased. Can be high.

  The silicon oxide particles are not particularly limited, and examples thereof include silica produced by a dry method such as fumed silica and fused silica, and silica produced by a wet method such as colloidal silica, sol-gel silica and precipitated silica. It is done. Among these, fumed silica is suitably used as the silicon oxide particles from the viewpoint of obtaining a sealant with less volatile components and higher transparency.

Examples of the fumed silica include Aerosil 50 (specific surface area: 50 m ² / g), Aerosil 90 (specific surface area: 90 m ² / g), Aerosil 130 (specific surface area: 130 m ² / g), Aerosil 200 (specific surface area). : 200 m ² / g), Aerosil 300 (specific surface area: 300 m ² / g), Aerosil 380 (specific surface area: 380 m ² / g) (all manufactured by Nippon Aerosil Co., Ltd.) and the like.

  The organosilicon compound is not particularly limited. For example, a silane compound having an alkyl group, a silicon compound having a siloxane skeleton such as dimethylsiloxane, a silicon compound having an amino group, and a silicon compound having a (meth) acryloyl group. Examples thereof include a compound and a silicon compound having an epoxy group. The “(meth) acryloyl group” means an acryloyl group and a methacryloyl group.

  From the viewpoint of further enhancing dispersibility of the silicon oxide particles, the organosilicon compound is selected from the group consisting of an organosilicon compound having a dimethylsilyl group, an organosilicon compound having a trimethylsilyl group, and an organosilicon compound having a polydimethylsiloxane group. It is preferable that at least one selected.

  As an example of a surface treatment method using an organosilicon compound, when an organosilicon compound having a dimethylsilyl group or an organosilicon compound having a trimethylsilyl group is used, for example, dichlorodimethylsilane, dimethyldimethoxysilane, hexamethyldisilazane, trimethylsilyl A method of surface-treating silicon oxide particles using chloride, trimethylmethoxysilane, or the like can be given. In the case of using an organosilicon compound having a polydimethylsiloxane group, a method of surface-treating silicon oxide particles using a compound having a silanol group at the terminal of the polydimethylsiloxane group, cyclic siloxane, or the like can be mentioned.

Examples of commercially available silicon oxide particles surface-treated with the above organosilicon compound having a dimethylsilyl group include R974 (specific surface area: 170 m ² / g) and R964 (specific surface area: 250 m ² / g) (both Nippon Aerosil Etc.).

Commercially available silicon oxide particles surface-treated with the above organosilicon compound having a trimethylsilyl group include RX200 (specific surface area: 140 m ² / g) and R8200 (specific surface area: 140 m ² / g) (both from Nippon Aerosil Co., Ltd.) Manufactured) and the like.

RY200 (specific surface area: 120 m ² / g) (manufactured by Nippon Aerosil Co., Ltd.) and the like can be mentioned as a commercial product of silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group.

  The method for surface-treating the silicon oxide particles with the organosilicon compound is not particularly limited. As this method, for example, a dry method in which silicon oxide particles are added to a mixer and an organosilicon compound is added while stirring, a slurry method in which an organosilicon compound is added to a slurry of silicon oxide particles, and silicon oxide particles And a direct treatment method such as a spray method in which an organosilicon compound is sprayed after drying. Examples of the mixer used in the dry method include a Henschel mixer and a V-type mixer. In the dry method, the organosilicon compound is added directly or as an alcohol aqueous solution, an organic solvent solution or an aqueous solution.

  In order to obtain silicon oxide particles surface-treated with the organosilicon compound, when preparing a sealant for an optical semiconductor device, the silicon oxide particles and the matrix resin such as the first and second silicone resins An integral blend method in which an organosilicon compound is directly added during mixing may be used.

  The content of the silicon oxide particles is preferably 0.1 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight in total of the first silicone resin and the second silicone resin. The content of the silicon oxide particles is more preferably 0.5 parts by weight or more, still more preferably 1 part by weight or more with respect to 100 parts by weight of the total of the first silicone resin and the second silicone resin. More preferably, it is 35 weight part or less, More preferably, it is 20 weight part or less. When the content of the silicon oxide particles is equal to or higher than the lower limit, it is possible to suppress a decrease in viscosity at the time of curing. When the content of the silicon oxide particles is not more than the above upper limit, the viscosity of the sealant can be controlled to a more appropriate range, and the transparency of the sealant can be further enhanced.

(Phosphor)
The encapsulant for optical semiconductor devices according to the present invention may further contain a phosphor. The above phosphor acts to absorb light emitted from a light emitting element that is sealed using a sealant for an optical semiconductor device and generate fluorescence to finally obtain light of a desired color. To do. The phosphor is excited by light emitted from the light emitting element to emit fluorescence, and light of a desired color can be obtained by a combination of light emitted from the light emitting element and fluorescence emitted from the phosphor.

  For example, when it is intended to finally obtain white light using an ultraviolet LED chip as a light emitting element, it is preferable to use a combination of a blue phosphor, a red phosphor and a green phosphor. When it is intended to finally obtain white light using a blue LED chip as a light emitting element, it is preferable to use a combination of a green phosphor and a red phosphor, or a yellow phosphor. As for the said fluorescent substance, only 1 type may be used and 2 or more types may be used together.

The blue phosphor is not particularly limited. For example, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu and the like.

It is not particularly restricted but includes the red phosphor, for _{example, (Sr, Ca) S:} Eu, (Ca, Sr) 2 Si 5 N 8: Eu, CaSiN 2: Eu, CaAlSiN 3: Eu, Y 2 O 2 S : Eu, La ₂ O ₂ S: Eu, LiW ₂ O ₈ : (Eu, Sm), (Sr, Ca, Bs, Mg) ₁₀ (PO ₄ ) ₈ Cl ₂ : (Eu, Mn), Ba ₃ MgSi ₂ And O ₈ : (Eu, Mn).

The green phosphor is not particularly limited, and for example, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, SrGa ₂ S ₄ : Eu, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, SrSiON: Eu, ZnS: (Cu, Al), BaMgAl ₁₀ O ₁₇ (Eu, Mn), SrAl ₂ O ₄ : Eu, and the like.

Is not particularly restricted but includes the yellow phosphor, for _{example, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 Al 5 O 12: Ce, Tb 3 Al 5 O 12: Ce, CaGa 2 S 4: Eu , Sr ₂ SiO ₄ : Eu, and the like.

  Furthermore, examples of the phosphor include perylene compounds that are organic phosphors.

(Coupling agent)
The encapsulant for optical semiconductor devices according to the present invention may further contain a coupling agent in order to impart adhesiveness.

  It does not specifically limit as said coupling agent, For example, a silane coupling agent etc. are mentioned. Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxy. Examples include silane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. As for a coupling agent, only 1 type may be used and 2 or more types may be used together.

  The phosphor content can be adjusted as appropriate so as to obtain light of a desired color, and is not particularly limited. The content of the phosphor is preferably 0.1 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the encapsulant for optical semiconductor devices according to the present invention. The content of the phosphor is preferably 0.1 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of all components excluding the phosphor of the encapsulant for optical semiconductor devices.

(Other ingredients)
The encapsulant for optical semiconductor devices according to the present invention includes a dispersant, an antioxidant, an antifoaming agent, a colorant, a modifier, a leveling agent, a light diffusing agent, a thermally conductive filler, a flame retardant, and the like as necessary. The additive may be further contained.

  The first silicone resin, the second silicone resin, the silicon oxide particles, and the hydrosilylation reaction catalyst are prepared separately in a liquid containing one or more of them. The sealing agent for optical semiconductor devices according to the present invention may be prepared by mixing a plurality of liquids immediately before use. For example, liquid A containing the first silicone resin and hydrosilylation reaction catalyst and liquid B containing the second silicone resin are prepared separately, and liquid A and liquid B are mixed immediately before use. The encapsulant for optical semiconductor devices according to the present invention may be prepared. In this case, the silicon oxide particles and the phosphor may be added to the liquid A or the liquid B, respectively. Thus, the storage stability is improved by separately forming the first silicone resin and the hydrosilylation reaction catalyst and the second silicone resin into two liquids of the first liquid and the second liquid. Can be made.

(Details and applications of sealants for optical semiconductor devices)
The curing temperature of the encapsulant for optical semiconductor devices according to the present invention is not particularly limited. The preferable lower limit of the curing temperature of the encapsulant for optical semiconductor devices is 80 ° C., the more preferable lower limit is 100 ° C., the preferable upper limit is 180 ° C., and the more preferable upper limit is 150 ° C. When the curing temperature satisfies the above preferable lower limit, curing of the sealant proceeds sufficiently. When the curing temperature satisfies the above preferable upper limit, the package is unlikely to be thermally deteriorated.

  The curing method is not particularly limited, but it is preferable to use a step cure method. The step cure method is a method in which the resin is temporarily cured at a low temperature and then cured at a high temperature. By using the step cure method, curing shrinkage of the sealant can be suppressed.

  The method for producing the encapsulant for optical semiconductor devices according to the present invention is not particularly limited, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a three roll or a bead mill, Examples thereof include a method of mixing the first silicone resin, the second silicone resin, the hydrosilylation reaction catalyst, and other components blended as necessary at room temperature or under heating.

  The light emitting element is not particularly limited as long as it is a light emitting element using a semiconductor. For example, when the light emitting element is a light emitting diode, for example, a structure in which a semiconductor material for LED type is stacked on a substrate can be given. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

  Examples of the material for the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Further, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the material of the buffer layer include GaN and AlN.

  Specific examples of the optical semiconductor device according to the present invention include a light emitting diode device, a semiconductor laser device, and a photocoupler. Such optical semiconductor devices include, for example, backlights such as liquid crystal displays, illumination, various sensors, light sources such as printers and copiers, vehicle measuring instrument light sources, signal lights, indicator lights, display devices, and light sources for planar light emitters. , Displays, decorations, various lights, switching elements and the like.

  In the optical semiconductor device according to the present invention, the light emitting element formed of the optical semiconductor is sealed with the cured product of the encapsulant for optical semiconductor devices according to the present invention. In the optical semiconductor device according to the present invention, a cured product of an encapsulant for optical semiconductor devices is arranged so as to seal a light emitting element formed of an optical semiconductor such as an LED. For this reason, it is hard to produce a crack in the hardened | cured material of the sealing compound for optical semiconductor devices which has sealed the light emitting element, it is hard to peel from a package, and improves light transmittance, heat resistance, a weather resistance, and gas barrier property. be able to.

(Embodiment of optical semiconductor device)
FIG. 1 is a front sectional view showing an optical semiconductor device according to an embodiment of the present invention.

  The optical semiconductor device 1 of this embodiment has a housing 2. An optical semiconductor element 3 made of LEDs is mounted in the housing 2. The optical semiconductor element 3 is surrounded by an inner surface 2 a having light reflectivity of the housing 2. In the present embodiment, the optical semiconductor element 3 is used as a light emitting element formed of an optical semiconductor.

  The inner surface 2a is formed so that the diameter of the inner surface 2a increases toward the opening end. Therefore, of the light emitted from the optical semiconductor element 3, the light that has reached the inner surface 2 a is reflected by the inner surface 2 a and travels forward of the optical semiconductor element 3. In a region surrounded by the inner surface 2 a so as to seal the optical semiconductor element 3, an optical semiconductor device sealing agent 4 is filled. The encapsulant 4 for optical semiconductor devices is a cured product of the encapsulant for optical semiconductor devices.

  The structure shown in FIG. 1 is merely an example of an optical semiconductor device according to the present invention, and the mounting structure of the optical semiconductor element 3 can be modified as appropriate.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

(Synthesis Example 1) Synthesis of First Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 94 g of trimethylmethoxysilane, 99 g of dimethyldimethoxysilane, 92 g of diphenyldimethoxysilane, and 133 g of vinyltrimethoxysilane And stirred at 50 ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 108 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution and heated under reduced pressure. Thereafter, potassium acetate was removed by filtration to obtain a polymer (A).

The number average molecular weight (Mn) of the obtained polymer (A) was 1800. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (A) had the following average composition formula (A1).

(Me ₃ SiO _1/2 ) _0.29 (Me ₂ SiO _2/2 ) _0.27 (Ph ₂ SiO _2/2 ) _0.13 (ViSiO _3/2 ) _0.31 ... Formula (A1)

  In the above formula (A1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (A) was 21 mol%.

(Synthesis Example 2) Synthesis of Second Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 31 g of trimethylmethoxysilane, 50 g of 1,1,3,3-hexamethyldisiloxane, dimethyldimethoxy 140 g of silane, 59 g of diphenyldimethoxysilane, 48 g of phenyltrimethoxysilane, and 45 g of vinyltrimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 1.4 g of hydrochloric acid and 92 g of water was slowly added dropwise, and after the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by heating under reduced pressure to remove volatile components. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (B) was obtained.

The number average molecular weight (Mn) of the obtained polymer (B) was 600. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (B) had the following average composition formula (B1).

(Me ₃ SiO _1/2 ) _0.09 (HMe ₂ SiO _1/2 ) _0.24 (Me ₂ SiO _2/2 ) _0.38 (Ph ₂ SiO _2/2 ) _0.08 (PhSiO _3/2 ) _0.10 (ViSiO _3/2 ) _0.10 Formula (B1)

  In the above formula (B1), Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (B) was 23 mol%.

(Synthesis Example 3) Synthesis of First Organopolysiloxane In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 476 g of dimethyldimethoxysilane and 5.3 g of vinylmethyldimethoxysilane were added and stirred at 50 ° C. did. A solution prepared by dissolving 2.2 g of potassium hydroxide in 144 g of water was slowly added dropwise thereto, and after the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, volatile components were removed under reduced pressure, 2.4 g of acetic acid was added to the reaction solution, and the mixture was heated under reduced pressure. Thereafter, potassium acetate was removed by filtration to obtain a polymer (C).

As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (C) had the following average composition formula (C1).

(Me ₂ SiO _2/2 ) _0.99 (ViMeSiO _2/2 ) _0.01 ... Formula (C1)

  In the above formula (C1), Me represents a methyl group, and Vi represents a vinyl group.

  The content ratio of the phenyl group of the obtained polymer (C) was 0 mol%.

(Synthesis Example 4) Synthesis of Second Organopolysiloxane 24 g of 1,1,3,3-tetramethyldisiloxane and 438 g of dimethyldimethoxysilane were added to a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer. And stirred at 50 ° C. Into this, a solution of 2.0 g of hydrochloric acid and 134 g of water was slowly added dropwise. After the addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by heating under reduced pressure to remove volatile components. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (D) was obtained.

As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (D) had the following average composition formula (D1).

(HMe ₂ SiO _1/2 ) _0.08 (Me ₂ SiO _2/2 ) _0.92 Formula (D1)

  In the above formula (D1), Me represents a methyl group.

Example 1
Polymer A (10 g), Polymer B (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (platinum metal is 10 ppm by weight with respect to the whole sealant) Amount) and 0.4 g of silicon oxide fine particles (AEROSIL RY200, silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group, specific surface area 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd.) The sealing agent for optical semiconductor devices was obtained.

(Example 2)
Polymer A (10 g), Polymer B (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (platinum metal is 10 ppm by weight with respect to the whole sealant) Amount) and ² g of silicon oxide fine particles (AEROSIL R8200, silicon oxide particles surface-treated with an organosilicon compound having a trimethylsilyl group, specific surface area 140 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), defoaming, light A sealant for a semiconductor device was obtained.

(Example 3)
Polymer A (10 g), Polymer B (10 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (platinum metal is 10 ppm by weight with respect to the whole sealant) Amount) and 1.0 g of silicon oxide fine particles (R974, silicon oxide particles surface-treated with an organosilicon compound having a dimethylsiloxane group, specific surface area 170 m ² / g, manufactured by Nippon Aerosil Co., Ltd.) and defoaming The sealing agent for optical semiconductor devices was obtained.

(Comparative Example 1)
Polymer C (16 g), Polymer D (4 g), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (platinum metal is 10 ppm by weight with respect to the whole sealant) Amount) and ² g of silicon oxide fine particles (AEROSIL R8200, silicon oxide particles surface-treated with an organosilicon compound having a trimethylsilyl group, specific surface area 140 m ² / g, manufactured by Nippon Aerosil Co., Ltd.), defoaming, light A sealant for a semiconductor device was obtained.

(Light transmittance)
The obtained encapsulant for optical semiconductor devices was cured at 130 ° C. for 3 hours to obtain a cured product having a length of 50 mm × width of 50 mm × thickness of 1 mm. The light transmittance at 400 nm of the obtained cured product was measured using “U-4000” manufactured by Hitachi, Ltd.

(Refractive index of cured product)
The obtained encapsulant for optical semiconductor devices was cured at 130 ° C. for 3 hours to obtain a cured product having a length of 20 mm × width of 20 mm × thickness of 50 μm. The refractive index at a wavelength of 589 nm of the obtained cured product was measured using a digital Abbe refractometer (manufactured by Elma).

(Preparation of phosphor-containing sealant)
Phosphor powder (volume average particle size 17 μm, specific gravity 4.7, “EY4453”, manufactured by Intematix) 0.8 to 10 parts by weight of each encapsulant for optical semiconductor devices obtained in Examples and Comparative Examples Part by weight was added, stirred, and degassed to obtain an optical semiconductor device sealant (hereinafter sometimes referred to as a phosphor-containing sealant).

(Brightness evaluation)
Light in which a light emitting element having a main emission peak of 460 nm is mounted on a silver-plated polyphthalamide housing material with a lead electrode by a die bond material, and the light emitting element and the lead electrode are electrically connected by a gold wire The obtained phosphor-containing sealant was injected into a semiconductor element, and was cured by heating at 130 ° C. for 3 hours, thereby producing 50 optical semiconductor devices.

  A current of 50 mA was passed through each of the light emitting elements in the 50 optical semiconductor devices at 23 ° C., and the light intensity was measured using an optical measurement device (OL770, manufactured by Optronic Laboratories). The case where the average value of 50 pieces was 4.8 cd or more was judged as “◯”, and the case where it was less than 4.8 cd was judged as “x”.

  The results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Housing 2a ... Inner surface 3 ... Optical semiconductor element 4 ... Sealant for optical semiconductor devices

Claims (6)

A first silicone resin having an aryl group and an alkenyl group (except a silicone resin having a hydrogen atom bonded to a silicon atom);
A second silicone resin having a hydrogen atom bonded to an aryl group and a silicon atom;
Silicon oxide particles surface-treated with an organosilicon compound;
A catalyst for hydrosilylation reaction,
The sealing compound for optical semiconductor devices whose refractive index of the hardened | cured material after hardening is 1.450-1.470. The first silicone resin is a first silicone resin represented by the following formula (1A) and having an aryl group and an alkenyl group (excluding a silicone resin having a hydrogen atom bonded to a silicon atom);
2. The encapsulating for optical semiconductor devices according to claim 1, wherein the second silicone resin is a second silicone resin represented by the following formula (51A) and having a hydrogen atom bonded to an aryl group and a silicon atom. Agent.

In the formula (1A), a, b and c are a / (a + b + c) = 0 to 0.50, b / (a + b + c) = 0.40 to 1.0 and c / (a + b + c) = 0 to 0. 50, R1 to R6 represent at least one aryl group, at least one represents an alkenyl group, and R1 to R6 other than the aryl group and the alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. .

In the formula (51A), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. 20 to 0.80 are satisfied, R51 to R56 each represent at least one aryl group, at least one represents a hydrogen atom bonded to a silicon atom, and R51 to R51 other than an aryl group and a hydrogen atom bonded to a silicon atom R56 represents a hydrocarbon group having 1 to 8 carbon atoms. The content ratio of the aryl group calculated | required from the following formula (X) in the said 1st silicone resin and the said 2nd silicone resin is 10 mol% or more and less than 30 mol%, respectively. Sealant for optical semiconductor devices.
Aryl group content ratio (mol%) = (average number of aryl groups contained in one molecule of the first silicone resin or the second silicone resin × the molecular weight of the aryl group / the first silicone resin or the above Number average molecular weight of second silicone resin) × 100 Formula (X)   The organosilicon compound is at least one selected from the group consisting of an organosilicon compound having a dimethylsilyl group, an organosilicon compound having a trimethylsilyl group, and an organosilicon compound having a polydimethylsiloxane group. The sealing agent for optical semiconductor devices of any one of these. It is obtained by curing the sealant for optical semiconductor devices according to any one of claims 1 to 4,
Hardened | cured material of the sealing compound for optical semiconductor devices whose refractive index is 1.450-1.470. An optical semiconductor element, and a cured product of an encapsulant for optical semiconductor devices provided to seal the optical semiconductor element,
An optical semiconductor device, wherein the cured product of the encapsulant for optical semiconductor devices is formed by curing the encapsulant for optical semiconductor devices according to any one of claims 1 to 4.

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